Ultra low loss dielectric thermosetting resin compositions and high performance laminates manufactured therefrom

ABSTRACT

A ultra low loss dielectric thermosetting resin composition has at least one cyanate ester component (A) and at least one reactive intermediate component (B) that is capable of copolymerization with said component (A). The invention is a cyanate ester resin of the form: T n -[W—(Z) f /(H) 1-f —W] n−1 —[W—(Z) f /(H) 1-f —(OCN) f /(R) 1-f ] n+2 , wherein T is a 1,3,5-substituted-triazine moiety (C 3 N 3 ); W is a linking atom between triazine and either component A or component B; Z is component (A): H is component (B); OCN is a cyanate ester end group; R is a reactive end group of component B; n is an integer greater than or equal to 1; and f is a weight or mole fraction of component A. The composition exhibits excellent dielectric properties and yields a high performance laminate for use in high layer count, multilayer printed circuit board (PCB), prepregs, resin coated copper (RCC), film adhesives, high frequency radomes, radio frequency (RF) laminates and various composites.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to thermosetting resin compositions that areuseful as high performance and high layer count, multilayer printedcircuit board (PCB), prepregs, resin coated copper (RCC), filmadhesives, high frequency radomes, radio frequency (RF) laminates andvarious other composites made from resin compositions.

2. Description of the Prior Art

Advances in electronic devices continue to approach the limit of printedcircuit board (PCB) technologies. The performance requirements forcomposite and laminate materials are becoming more stringent. In the“cloud computing”, Smartphone industries and wireless communication (4 Gand 4G LET Advanced) for example, high speed high frequency circuitsrequire substrates with difficult to attain electrical properties, suchas ultra low dielectric loss and low dielectric constant. Currentcomposite materials fail to meet some of the most critical requirementssuch as dielectric loss in high-speed communications. As frequencyincreases, the amount of signal loss to the substrate becomes moresignificant. As a result, materials are required that will give PCBs therequired electrical properties for rapid transmission of high frequencysignals with signals integrity, while maintaining the thermal, physicaland mechanical properties desirable for PCBs.

Various composite materials employed include Polytetrafluoroethyene(PTFE). Although PTFE is an excellent low dielectric material, itsuffers from significant processing problems such as a lack of fluiditydue to high melt temperature and viscosity; the inability to formmultilayer boards (high layer count) and low glass transitiontemperature (Tg). These processing problems limit PTFE use in radiofrequency (RF) applications and limited multilayer digital substrateapplications. PTFE is also a high price material, which furtherprohibits its use in the mass production of consumer electronics.

Epoxy resins on other hand are the industry standard for PCB manufacturedue to low cost and good processing conditions. However poor electricproperties and low glass transition (Tg) limit epoxy to use as highspeed communication and high temperature integrated circuit (IC)substrates suitable for tablets and other computing industries. The mostcommon mass production epoxy laminates are FR-4, FR-5 and variousenhanced epoxies.

Another composite material employed includes Cyanate esters (CE) whichare known for generating thermoset materials with mid range dielectricconstants and dielectric loss properties. CEs are considered useful forhigh performance substrate applications. Benefits of these materialsinclude process-ability similar to epoxy laminates (FR-4) and goodthermal properties in dry conditions.

However, cyanate resins have been disadvantageous in several aspects.Typical prior art cyanate resins include:

Blending CEs with thermoplastics and elastomers to form resins.Disadvantageously, this blend has been found to generatesemi-interpenetrating networks rather than uniform resins and oftencauses phase separation between cyanate and modifier domains. It hasbeen found that the use of hydroxylated polybutadiene (HPBD) inmodifying CEs by mixing/blending the two materials and directly curingthem generates a material with significant phase separation, whichresults in poor thermal resistance. It has further been determined thatliquid HPBD are incompatible with many CEs and that the use of acopolymer to combine and blend the materials is required.

Various elastomer modified cyanate esters exhibit low Tg and hightackiness and are unsuitable for multilayer boards. For example:

U.S. Pat. No. 4,780,507 to Gaku et al. discloses a thermosetting resincomposition comprising a thermosetting cyanate ester resin composition(A) and a butadiene based copolymer (B)(i) or an epoxy resin-modifiedbutadiene based copolymer (B)(ii), in which component (B)(i) or (B)(ii)are used for modifying component (A). Components are firstpre-polymerized into a resin and then form a non-tacky resinous materialby controlling the time and temperature of the reaction between thedifferent components. The use of solid polybutadiene-co-vinylaromaticpolymers to modify CEs is disclosed. However, these materials possessglass transition temperatures below 215° C.

U.S. Pat. App. Pub. 2013/0245161 A1 discloses resins incorporatingepoxies, cyanate esters and polybutadiene-styrene-divinylbenzeneterpolymers, however these suffer from extremely low Tgs between 100 and135° C. and high dissipation factors >0.005.

CN 101824157 to Baixing et al. discloses a method for modifying cyanateester resin by hydroxyl-terminated polybutadiene, which comprises thefollowing steps: adding hydroxyl-terminated polybutadiene rubber intothe cyanate ester resin with the addition quantity of 5 to 30 weightpercent; heating and melting the mixture to be uniformly mixed; heatingthe mixture to 120+/−15DEG C for pre-polymerization for 10 to 60 min;carrying out casting and curing; uniformly heating at 130 to 200 DEG Cfor 7 to 10 h for curing; and obtaining the modified cyanate esterresin. However, these CEs have been found to have low TG and hightackiness and thus lack usefulness in multilayer PCB technologies.

A significant drawback of CE resins is that they suffer from moistureuptake. Moisture plays a significant role in the failure of highfrequency applications. Water contributes high Dk (80) and has highpolarity; as a result even a small amount of water can have adetrimental effect on the physical and electrical properties ofsubstrate materials. If water reacts with the resin system it maycontribute to delamination during thermal performance. The resins of theinvention have reduced moisture uptake due to the reaction withmodifying resins.

Furthermore, the commercial CEs are brittle due to a tight networkstructure and as a result thin substrates made from CE are fragile fordrop tests in smart phone and other portable devices.

For examples, see:

U.S. Pat. No. 8,404,764 to Yu et al. discloses a resin compositioncomprising (A) 100 parts by weight of cyanate ester resin; (B) 5 to 25parts by weight of nitrogen and oxygen containing heterocyclic compound;(C) 5 to 75 parts by weight of polyphenylene oxide resin; and (D) 5 to100 parts by weight of oligomer of phenylmethane maleimide. By usingspecific components at specific proportions, the resin composition istaught to offer the features of low dielectric constant and lowdissipation factor and can be made into prepreg that may be used inprinted circuit board. Reports therein have been provided showing apolyphenylene oxide/cyanate ester resin that exhibits dissipationfactors near 0.0055, and which display Tgs below 185° C.

U.S. Pat. App. No. 20070203308A1 to Mori et al. and U.S. Pat. No.6,245,841 to Yeager et al. discloses curable compositions used incircuit boards, structural composite, encapsulating resins, and thelike, comprise at least one compound selected from the group consistingof cyanate esters and cyanate ester prepolymers, a flame retardant whichis substantially toluene soluble and substantially free of hydroxyresidues in the cured state, and a curing catalyst. Though issues ofmoisture properties were addressed, the processing of this product isdifficult using conventional procedures due to high melt viscosity.Furthermore, the thermoplastic (polyphenylene oxide, allyl, or liquidcrystal polymers (LCD)) is only soluble in exotic solvents (toluene,xylene, etc.).

U.S. Pat. No. 5,571,609 to Lawrence St. et al. discloses an electricalsubstrate material comprising a thermosetting matrix which includes apolybutadiene or polyisoprene resin and an unsaturated butadiene orisoprene containing polymer in an amount of 25 to 50 vol. %; a wovenglass fabric in an amount of 10 to 40 vol. %; a particulate, preferablyceramic filler in an amount of from 5 to 60 vol. %; a flame retardantand a peroxide cure initiator. A preferred composition has 18% wovenglass, 41% particulate filler and 30% thermosetting matrix. Theforegoing component ratios and particularly the relatively high range ofparticulate filler is an important feature of this invention in thatthis filled composite material leads to a prepreg which has very littletackiness and can therefore be easily handled by operators.Disadvantageously, this product is not suitable for high layer countboards due to the lack of adhesion of the hydrocarbon.

U.S. Pat. No. 7,425,371 discloses a thermosetting resin system thatappointed to be useful in the manufacture of high performance prepreg,laminate and composite materials as well as the prepregs, laminates andcomposites made from the thermosetting resin composition. The referencediscloses modifications of CEs with SMA but this composition lacks theelectrical performance for 4G and beyond applications, and no example isgiven to illustrate any benefit derived by modifying CE with SMA. Thelarge part of electrical properties was achieved by blending fusedsilica with epoxy, ester, elastomers such as SMA, and a flame retardant.Furthermore, the compositions claimed a chemically blended product, nota reaction intermediate.

Accordingly, there remains a need in the art for ultra low lossdielectric thermosetting resin compositions for high performancelaminates. Particularly needed in the art are ultra low loss dielectricthermosetting resin compositions for use in high performance and highlayer count, multilayer printed circuit board (PCB), prepregs, resincoated copper (RCC), film adhesives, high frequency radomes, radiofrequency (RF) laminates and various other composites made from resincompositions. Further needed in the art is a thermosetting resincomposition that exhibits excellent dielectric properties suitable butnot limited for 4G and 3rd Generation Partnership Project (3GPP).

SUMMARY OF THE INVENTION

The present invention provides ultra low loss dielectric thermosettingresin compositions for high performance laminates. Ultra low lossdielectric thermosetting resin compositions are provided for use in highperformance and high layer count, multilayer printed circuit board(PCB), prepregs, resin coated copper (RCC), film adhesives, highfrequency radomes, radio frequency (RF) laminates and various othercomposites made from resin compositions. Further provided is athermosetting resin composition that exhibits excellent dielectricproperties suitable but not limited for 4G and 3rd GenerationPartnership Project (3GPP).

More specifically, the invention provides a thermosetting resin havingthe form:

T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)

wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B. “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A.

The invention provides a thermosetting resin composition via chemicalattachment of:

-   -   a. at least one cyanate ester component (A);    -   b. at least one reactive intermediate component (B), said        component B being capable of copolymerization with said        component (A);

Component (A) is a member selected from the group consisting of2,2-bis(4-Cyanatophenyl) ispropylyidene, Bisphenol F Cyanate ester,Primaset PT resin, Primaset LECY and mixtures thereof. Preferably,component (A) is represented by the formula:

wherein X₁ and X₂ individually represent R and R is a member selectedfrom the group consisting of —CH(CH₃)—, —CH₂—, —C(CH₃)₂—,dicyclopentadiene (DCP), and functionalized DCP; n is an integer greaterthan 1; and Y represents at least one functional group.

Component B is a reactive modifier selected from the group consisting ofthermoplastics, small organic molecules, rubbers, andinorganic/organometallic polymers.

DETAILED DESCRIPTION OF THE INVENTION

The subject invention provides a thermosetting resin composition thatexhibits excellent dielectric properties suitable but not limited for 4Gand 3rd Generation Partnership Project (3GPP), which is a majorenhancement of the Long Term Evolution (LTE) standard. 4G-LTE-Advancedoffers a new wave of mobile functionality that will propel mobile speedand quality well into the future. 4G-LTE-Advanced offers peak data ratesof 1 Gbps compared to 300 Mbps on 4G-LTE and 10×-30× faster downloadspeeds than its predecessor. This speed can only be possible through thecombination of new software and hardware and new ultra-low DK/Dfmaterials, which play a significant role in maintaining signalintegrity. The power amplifier boards for 4G LET base station andback-panel in server, network gear, and Wi-Fi, require substrates withlow Dk/Df for new communication technologies. Besides electricalproperties, compositions providing excellent thermal, mechanical andother physical properties are necessary for these new technologies. Thesubject invention provides these novel compositions in order to addressthe electrical properties of these new technologies.

In the present invention a thermosetting resin composition is providedthat comprises at least one Cyanate ester (component A), one or morereactive intermediate (component B) which can undergo copolymerizationwith CE (component A). Furthermore, the final composition of theinvention is soluble in common organic solvents. Lower dielectric andgood mechanical properties, as well as, optional flame retardancyproperties were considered in the selection of the reactive intermediate(component B) to react with CE to form the thermosetting composition.When thermoplastic or elastomer modifiers are first reacted with thecyanate ester to generate a new polymeric material, a homogeneous systemcan be obtained.

The composition of the subject invention includes: a cyanate ester resinof the form:

T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)

Where:

T=1,3,5-substituted-triazine moiety (C₃N3);W=linking atom between triazine and either component A or component B;Z=Represents component A of the invention and comprises a cyanate esteras described below;H=Represents component B of the invention and comprises a reactivethermoplastic or other additive as described below;OCN=cyanate ester end group;R=Represents the reactive end groups of component B and may include butnot limited to groups such as: OH, SH, NH₂, Allyl, Vinyl, Phenol,Anhydrides, and Carboxylic acids;n is an integer greater than or equal to 1;f is the weight or mole fraction of component A in the invented resin;Where Z represents at least one Cyanate ester (component A) of theinvention.

Various CEs can be used including, but not limited to2,2-bis(4-Cyanatophenyl) ispropylyidene (available from Lonza undertrade name Primaset BADCY), Bis-(4-Cyanato-3,5-dimethylpheny)methane,Cyanated phenol-dicyclopentadine, Bis-(4-Cyanatophenyl)thioether,Bis(4-Cyanatophenyl) ether, 1,3Bis(4-Cyanatophenyl-1(1-methyehylidene)benzene, Resorcinol dicyanate,fused ring Cyanate monomers such as naphthalene and anthraquinone,Fluoroaliphatic dicyanates, Bisphenol F Cyanate ester, Primaset PTresin, Primaset LECY and mixtures thereof.

Where: X₁ and X₂ individually represent at least R, Ar, SO₂, O, or S. Ris selected from —CH, (CH₃)—, —CH₂—, —C(CH₃)₂—, dicyclopentadiene (DCP),and functionalized DCP; Ar is selected from functionalized ornon-functionalized benzene, biphenyl, naphthalene, phenol novolac,bisphenol A, bisphenol A novolac, bisphenol F, and bisphenol F novolac;n is an integer greater than 1; and Y represents functional groupsincluding but not-limited-to hydrogen, aliphatic groups, aromaticgroups, or halogens. Cyanate esters can be produce by anyone skilled inthe art by reaction of any phenol with cyanogen chloride in presence ofTEA at low temperature. Through extensive experimentation by way of thesubject invention, it has been surprisingly and unexpectedly discoveredthat a large fraction, 50% or greater, of Z is required in reaction withcomponent B to achieve thermal performance of resin compositions. Toachieve optimal dielectric properties 20% or greater B is required.

H representing component B of the invention is selected from reactivemodifiers. These additives include but are not limited tothermoplastics, small organic molecules, rubbers, andinorganic/organometallic polymers. The reactive groups on the additivesinclude but are not limited to hydroxyl groups, phenol groups, thiolgroups, epoxy groups, malemide groups, amines, thiols, thiophenols, andphosphorous groups. The additives my also contain secondary reactivegroups including but limited to allyls, vinyls, acrylates, halogens,ethyoxys, methoxys and acetylenes. The thermoplastic additives includebut are not limited to hydroxylated polybutadiene (HPBD) with molecularweights between 100 and 10,000 g/mol such as Krasol LBH 2000, Krasol LBH3000, Krasol LBH-P 2000, Krasol LBH-P 3000, Poly bd R-45HTLO, Poly bdR-20LM from Cray Valley; G-1000, G-2000, G-3000 from Nippon-Soda;Hydrogenated hydroxylated polybutadiene (HHPBD) such as KrasolHLBH-P2000, Krasol HLBH-P3000 from Cray Valley, GI-1000, GI-2100,GI-3000 and epoxidized polybutadienes and epoxidized hydroxylatedpolybutadiene; reactive polydimethylsiloxane (PDMS) with molecularweights between and including 100-20,000 g/mol and at least 2 functionalgroups per molecule of either hydroxyl or epoxy groups such as Silmer OHC50; OH J10; OH Di-10; OH Di-50; EP C50; EP J10; Di-50; EP Di-100 bySiltech; or polymethylphenylsiloxane containing between 3-9% OHfunctional groups such as silres 604 by Wacker. Reactivefluoro-modifiers include but are not limited to fluorinatedthermoplastics such as reactive polyvinylidene fluoride (PVDF), modifiedfluoroethylene vinyl ether (FEVE) such as Lumiflon, and fluorinatedhydrocabons such as but not limited to HO—(CF₂CF₂)_(n)-OH wheren=integer ≧1. Other reactive modifiers include Cardinol, phenolterminated polyphenylphosphonate (Fyrol-PMP, Nofia), DOPO, Dantocol, DHE(from Lonza), silazanes, and reactive polyphosphazenes such asphenol-modified polyphenylenephosphazene, OCN-R-NCO and its prepolymers,PPO derivatives such as SA-900 and SA-9000 from Sabic, Primaset™ PPI-600from Lonza.

Heretofore disclosed and utilized compositions and methods have shownthat liquid hydroxylated polybutadienes cannot modify cyanate esters dueto the incompatibilities between the two substances. As describedpreviously, this results in significant phase separation in resins andreduced thermal and electrical properties in the cured materials.However, it has been surprisingly and unexpectedly found by way of thesubject invention through extensive experimentation that with the properratio and structure of the HPBD a homogenous resin and cured materialwith high Tg and low dielectric properties could be prepared. In thisinvention when liquid HPBD is used as component B it comprises linearand branched liquid HBPD (preferably linear HPBD) with hydroxylfunctionalities between 2-3, preferably 2 and molecular weights between500 Da and 100,000 Da, preferably between 1000 Da and 5000 Da withpolydispersities between 1 and 3, preferably between 1 and 2.5. Furtherthe liquid HPBD must possess 1° alcohol or 2° alcohol end groupspreferably 10 alcohols to react with component A. For optimal propertiesthe liquid HPBD when used as component B should have between 10-90% 1,2vinyl groups, preferably between 20-75% and a ratio of 1,4-trans to1,4-cis groups between 3:1 to 1.8:1.

Surprising and unexpectedly, the component B used has very low Tg but ithas unexpectedly been found that with a properly selected ratio ofcomponent A to component B, the reaction product or composition of thesubject invention yields very high Tg. The component B used to producethe resin composition possesses low dielectric properties, low moisturesusceptibility; low CTE and good mechanical properties. When the resinof the subject invention is fully cured weakness of Cyanate esters areeliminated. Some component B, such as hydrocarbon elastomers, mayrequire flame retardant materials to pass V0 of laminates. Component Branges from about 5%-50%, preferably from about 10%-35%, and mostpreferably from about 20%-35%. Component B present is preferably 20% andmost preferably 30%. Preferably, the content of each component in theresin comprises 50-95 wt % component A; 5-50 wt %, preferably between15-30 wt % component B, and can contain up to 30 wt % flame-retardant.

The resin composition of the present invention may be prepared throughthe following procedure:

The selected component A is heated between 135° C. and 200° C.,preferably between 175° C. and 190° C. for between 1 and 5 hourspreferably 2-3 hrs. In the next step component B is warmed to 130° C.and added into component A. The reaction mixture is then heated tobetween 100° C. and 195 OC, preferably between 110° C. and 135° C. andstirred to react each component together. The progress of the reactionis followed by monitoring the viscosity and refractive index of theresin at 95° C. The reaction is considered complete when the viscosityof the resin at 95° C. is between 100 cP and 200,000 cP, preferablybetween 2500 cP and 90,000 cP, the reaction is cooled to stop thereaction to give the neat resin. Alternatively, one or more solvents canbe optionally incorporated into the new thermosetting resin inventioncomposition in order to quench the reaction and control resin viscosity

With the addition of solvent, care should be taken to make sure there isno phase separation and a homogeneous resin is obtained upondissolution. Any solvent known by one with skill in the art to be usefulin conjunction with resin composition can be used. Particularly usefulsolvents include methyl ethyl ketone (MEK), xylene, toluene, DMF, andmixtures thereof. MEK is the most preferred solvent for this invention.When used, solvents are present in the thermosetting resin in the amountof 10-60%, preferably 15-30% and most preferably 20-25% by weight. Theviscosity of the resin solution at room temperature should be between50-1000 cP, preferably between 200-600 cP.

The resins of the invention can be cured into a solid material by heat,with or without a catalyst. Component B of the invention not onlyimproves the physical and electrical properties of the final resin butalso acts as a catalyst of the curing of the cyanate ester. Therefore,the curing of the resin of the subject invention occurs at asignificantly reduced temperature compared to conventional cyanateresin. The addition of ppm level metal complex salts such asNovocure-200 (available from Novoset, LLC, NJ) to the invention furtherreduces the curing temperature and time.

For example, the resins in this invention can be heated between 120° C.and 190° C. for between 30 min and 240 min, preferably between 150 and175° C. for between 60 min and 180 min. The invention can then be heatedbetween 200-235° C. for 30 min to 240 min, preferably between 220-235°C. for 30 min to 120 min. Additionally, the subject resin can be furtherpost-cured at temperature between 245-260° C. for 30 min to 180 min. Theresins of the subject invention, when fully cured, generate solidthermoset materials that possess glass transition temperatures (T_(g))between 180° C. and 400° C. and Tan 6 between 200° C. and 500° C. Thethermosetting resin compositions of the present invention can beformulated with, for example but not limited to, epoxy, SMA, PPO, APPEfillers, cured CEs or new resin composition as dielectric fillers,catalyst, and one or more flame retardant. The most common commercialflame-retardants would be suitable for new composition. Also resinlaminates made from resin composition can be made Vo without halogenatedflame retardant using reactive phosphorus flame-retardants such asFyrol-PMP, DOPO, DOPO-HQ, Nofia or below structure as well asnon-reactive phosphorous flame-retardants.

One or more catalysts are optionally added to the thermosetting resincompositions of present invention in order to enhance the rate ofcuring. The catalyst chosen may be suitable for CE curing such as cobaltor copper acetylacetonate, cobalt or copper octanoate, etc. or a mixturethereof. Depending on invented resin composition, other optionalcatalysts can include free radical catalyst such as dicumyl peroxide,the catalyst level range from ppm levels to less than 3 wt % dependingon the catalysis used.

The thermosetting resin compositions of the subject invention alsoprovide prepregs with or without tack. The compositions are particularlyuseful in preparation high Tg laminates with no phase separation havingultra low dielectric constants and ultra low dielectric loss. Theseelectrical properties help solve signal speed and signal integrityproblem encountered with high-speed analog and digital circuitryapplications.

The thermosetting resin compositions of the subject invention are usefulfor making prepregs in continuous process with or without solvent. Theviscosity of the inventive compositions can be adjusted for hot/meltprepreg and present substantial cost savings for prepreg production.Prepregs are generally manufactured using a core material including butnot limited to a roll of woven glass, carbon, Kevlar, spectra, aramid,or quartz fibers. The thermosetting resin composition can also be coateddirectly to any polymeric film for the Build-up PCB. It can also bedirectly coated to copper using slot-die or other related coatingtechniques for resin-coated copper (RCC).

The prepreg materials made from the present composition can be convertedto laminates. The lamination process typically follows the stack-up ofone or more prepreg layers between one or more sheets of conductive foilsuch as copper foil. This process is often described as copper cladlaminates (CCL) and is generally well known to persons with ordinaryskill in the art. Pressure and temperature applied to the prepreg stackresult in the formation of laminates. The laminates produce from thecurrent invention exhibits high Tg without any phase separation.Depending on compositions of the current invention, it is also possibleprepare laminates of moderate Tg (>150C) with considerable flexibility.Flexible laminates are very useful for various bendable electronicdevices.

Examples 1-20

The following examples are presented to provide a more completeunderstanding of the invention. The specific techniques, conditions,materials, proportions and reported data set forth to illustrate theprinciples and practice of the invention are exemplary and should not beconstrued as limiting the scope of the invention.

Example 1

100.1846 g BADCy (available from Lonza) was heated to 190° C. andstirred for 2 hours to reduce crystallinity. The reaction mixture wascooled to 175° C. and 43.2751 g 20 HPBD added in two portions. After theaddition of the first 20.3303 g the temperature of the reaction mixturedropped to 158° C., the mixture was heated up to 160-170° C. and thesecond 22.3303 g of 2° HPBD was added (dropping the temperature to 138°C.). The mixture was heated back to 173° C. and the reaction terminatedat 600 cP at 95° C.

Example 2

8.8653 g of BADCy and 3.7820 g of 2° HPBD were combined at roomtemperature and slowly warmed to 130° C. The reaction mixture wasstirred at this temperature until a resin viscosity of 720 cP at 95° C.was reached. The resin was poured into a container and allowed to coolto room temperature. The solid resin was melted and pressed betweenplatens at 250 psi. The resin was cured with novoCure (150 ppm activemetal) for 45 min at 150° C. followed by 2 hours at 235° C. followed bya post cure for 2 hours at 260° C. Tg=241° C.

Example 3

4.9072 g BADCy, 6.0641 g METHYLCy (available from Lonza), and 4.7156 gof 2° HPBD were combined at room temperature to form a white slurry. Theslurry was heated to 184° C. to melt the cyanate esters and initiate thereaction. The reaction was terminated by cooling to room temperaturewhen the resin viscosity reached 1200 cP at 95° C.

Example 4

7.928 g BADCy, 0.2261 g SMA and 3.2855 g, 2° HPBD were combined as aslurry at room temperature. The slurry was warmed to 150° C. and stirreduntil the SMA dissolved. The reaction mixture was then heated to 180° C.and the reaction continued until a viscosity of 5000 cP was reached at95° C. Cooling to room temperature gave a tacky end product. The neatresin was cured for 2 hours at 150° C. followed by 2 hours at 235° C.followed by a post cure for 2 hours at 260° C. Tg=167° C.

Example 5

7.9728 g BADCy, 1.10191 SAM 2.0948 g 2° HPBD were combined at roomtemperature and heated to 174° C. to with stirring dissolve allmaterials and initiate the reaction. The temperature was then reduced to137° C. and stirred for 8.5 hrs to give the final tacky semi-solidmaterial

Example 6

8.6658 g DT4000 (available from Lonza) and 5.8277 2° HBPD combined atroom temperature and heated to 160° C. to dissolve the HBPD into themolten DT4000. The reaction mixture was then heated and stirred between180° C. and 195° C., until a resin viscosity of 700 cP was reached at95° C.

Example 7

212.0447 g BADCy and 53.1177 g 1° HPDB were combined at room temperatureand heated to 150° C. to melt the CE and combine with HPDB. The reactionmixture was stirred at this temperature for 8.5 hours. When the resinviscosity reached 7658 cP at 95° C., the resin was allowed to cool to100° C. and MEK was added to generate a resin solution with a viscosityof 400 cP with a solid content of 75%.

Example 8

309.8981 g BADCy and 77.8439 g 1° HPBD combined at room temperature toform a slurry. The reaction mixture was then heated to 182° C. for 1.5hour. The temperature was reduced to 153° C. for an addition 2.5 hours.When the resin viscosity reached 4545 cP at 95° C., the reaction mixturewas removed from heat and allowed to cool to 100° C. and MEK was addedto generate a resin solution with a solid content of 80% and a viscosityof 450 cP at 25° C.

Example 9

11.0493 g DT4000 and 78.5732 g 1° HPBD were heated with stirring to 170°C. to dissolve the HBPD into the DT4000 generating a clear solution. Thereaction was stirred at temperature until the resin viscosity at 95° C.reached 2444.19, at which point the reaction was removed from heat andallowed to reach 95° C. Upon cooling the resin begins to cloud. Theaddition of MEK resulted in a clear dark brown solution. The resin wascured at 150° C. for 2 hours followed by 235° C. for 2 hours and postcured for 2 hours at 250° C. Tg=143° C.

Example 10

In a 1 L reaction kettle 800 g BADCy was heated to 130° C. at whichpoint 200 g HPBD was added with stirring. This mixture was heatedbetween and 195° C. and stirred. The reaction is terminated when theresin viscosity at 95° C. is 6000. The resin was cured at 150° C. for 2hours followed by 235° C. for 2 hours and post cured for 2 hours at 250°C. Tg=241° C.

Example 11

In a 1 L reaction kettle 800 g METHYLCy was heated to 130° C. at whichpoint 200 g of 1° HPBD was added with stirring. This mixture was heatedto 140° C. and stirred until the resin viscosity at 95° C. reached 9281cP. The reaction mixture was removed from heat and allowed to cool toroom temperature give a clear, orange, tackles material.

Example 12

In a 1 L reaction kettle 800 g PT-3° (available from Lonza) was heatedto 130° C. at which point 200 g HPBD was added with stirring. Thismixture was heated between 120° C. and 195° C. and stirred. The reactionis terminated when the resin viscosity at 95° C. is 12 000 cP.

Example 13

In a 1 L reaction kettle 800 g BADCy was heated to between 175° C. and195° C. for 2 hours at which point the reaction was cooled to 130° C.and 200 g HPBD (warmed to 130° C.) was added with stirring. This mixturewas heated between 120° C. and 135° C. and stirred. The reaction isterminated when the resin viscosity at 95° C. is between 12 000 cP. Theresin was cured with novocure-200(150 ppm active metal) at 150° C. for 2hours followed by 235° C. for 2 hours and post cured for 2 hours at 250°C. Tg=280° C.

Example 14

In a 1 L reaction kettle 800 g of BADCy was heated to 130° C. to atwhich point 200 g of polysiloxane was added with stirring. This mixturewas heated between 120° C. and 155° C. and stirred. The reaction isterminated when the resin viscosity at 95° C. is between 5000 cP. Thereaction was cooled to 90° C. and MEK was added to generated a slightlyhazy yellow resin solution with a solid content of 85% and a resinviscosity of 110 cP. The resin was cured at 150° C. for 2 hours followedby 235° C. for 2 hours and post cured for 2 hours at 250° C. Tg=234° C.

Example 15

In a 1 L reaction kettle 800 g METHYLCy was heated to 130° C. at whichpoint 200 g polysiloxane was added with stirring. This mixture washeated between 120° C. and 155° C. and stirred. The reaction isterminated when the resin viscosity at 95° C. is between 500 cP and 30000 cP. The resin was cured at 150° C. for 2 hours followed by 235° C.for 2 hours and post cured for 2 hours at 250° C. Tg=240° C.

Example 16

In a 1 L reaction kettle 800 g DT-4000 was heated to 130° C. at whichpoint 200 g polysiloxane was added with stirring. This mixture washeated between 120° C. and 155° C. and stirred. The reaction wasterminated when the resin viscosity at 95° C. was 5425 cP. The reactionwas cooled to 95° C. and MEK was added to yield a clear dark resinsolution.

Example 17

In a 1 L reaction kettle 800 g BADCy was heated to 155° C. at whichpoint 200 g fluoropolymer was added with stirring. This mixture washeated to 155° C. and stirred. The reaction is terminated when the resinviscosity at 95° C. is 2500 cP. The resin was cured at 150° C. for 2hours followed by 235° C. for 2 hours and post cured for 2 hours at 250°C. Tg=266° C.

Example 18

In a 1 L reaction kettle 800 g METHYLCy was heated to 155° C. at whichpoint 200 g fluoropolymer was added with stirring. This mixture washeated to 165° C. and stirred. The reaction is terminated when the resinviscosity at 95° C. is between 8000 cP. The resin was cured at 150° C.for 2 hours followed by 235° C. for 2 hours and post cured for 2 hoursat 250° C. Tg=241° C.

Example 19

In a 1 L reaction kettle 700 g BADCy and 300 g cardinol were combinedand heated to 110° C. with stirring The reaction is terminated when theresin viscosity at 95° C. is 7250 cP.

Example 20

In a 1 L reaction kettle 800 g BADCy and 200 g DHE were combined andheated to 110° C. with stirring The reaction is terminated when theresin viscosity at 95° C. is 2125 cP and allowed to cool to 95° C. andMEK added to give a clear solution.

Having thus described the invention in rather full detail, it will beunderstood that such detail need not be strictly adhered to, but thatadditional changes and modifications may suggest themselves to oneskilled in the art, all falling within the scope of the invention asdefined by the subjoined claims.

What is claimed is: 1-31. (canceled)
 32. A method of making athermosetting resin composition, comprising the steps of: a. selectingat least one cyanate ester component (A) b. heating said component (A)to a given temperature for a time period; c. selecting at least onereactive intermediate component (B), said component B being capable ofcopolymerization with said component (A), said component (B) being athermoplastic selected from the group consisting of (i) hydroxylatedpolybutadiene (HPBD) with molecular weights between 100 and 10 000g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii)reactive polydimethylsiloxane (PDMS) with molecular weights between andincluding 100-20 000 g/mol and at least 2 functional groups per moleculeof either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxanecontaining between 3-9% OH functional groups; d. heating component (B);e. adding component (B) to component (A) to form a reaction mixture; f.heating said reaction mixture and stirring said reaction mixture toreact components together to form a resin; g. monitoring progress ofsaid reaction by monitoring viscosity and refractive index of said resinat a reaction temperature, said reaction being complete when saidviscosity of said resin at said reaction temperature is between 100 cPand 200,000 cP, wherein said resin is cooled to stop said reaction toyield a homogeneous resin of the form:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2) wherein T is a 1,3,5-substituted-triazine moiety (C₃N₃); W is a linkingatom between triazine and either component A or component B; Z iscomponent (A); H is component (B); OCN is cyanate ester end group; R isa reactive end group of component B; n is an integer greater than orequal to 1; and f is a weight or mole fraction of component A; saidthermosetting resin composition does not undergo phase separation, butinstead forms a neat, homogenous resin consisting of a triazineco-polymer that consists of component (A) and component (B) joinedthrough a triazine moiety;
 33. A method of making a thermosetting resincomposition as recited by claim 32, wherein said component (A) is heatedto temperatures between 135° C. and 200° C. for between 1 and 5 hours.34. A method of making a thermosetting resin composition as recited byclaim 32, wherein said component (B) is heated to about 130° C. andadded into component (A).
 35. A method of making a thermosetting resincomposition as recited by claim 32, wherein said reaction mixture isheated to between 100° C. and 195° C.
 36. A method of making athermosetting resin composition as recited by claim 32, wherein saidresin is completed when said viscosity of the resin at 95° C. is between100 cP and 200,000 cP.
 37. A method of making a thermosetting resincomposition as recited by claim 32, wherein at room temperature saidviscosity of said resin ranges between 50-1000 cP.
 38. A method ofmaking a thermosetting resin composition as recited by claim 32, whereincomponent B is a reactive modifier selected from the group consisting ofthermoplastics, small organic molecules, rubbers, andinorganic/organometallic polymers.
 39. A thermosetting resin compositionfor use in multilayer printed circuit boards for high performanceapplications defined by the formula:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B; “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A; wherein said thermosetting resin composition is formed bychemical reaction between: a. at least one cyanate ester component (A);and b. at least one reactive intermediate component (B), said componentB being capable of copolymerization with said component (A), saidcomponent (B) is a thermoplastic selected from the group consisting of(i) hydroxylated polybutadiene (HPBD) with molecular weights between 100and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD),(iii) reactive polydimethylsiloxane (PDMS) with molecular weightsbetween and including 100-20 000 g/mol and at least 2 functional groupsper molecule of either hydroxyl or epoxy groups, and (iv)polymethylphenylsiloxane containing between 3-9% OH functional groups;whereby said thermosetting resin composition does not undergo phaseseparation, but instead forms a neat, homogenous resin consisting of atriazine co-polymer that consists of component (A) and component (B)joined through a triazine moiety.
 40. A thermosetting resin compositionas recited by claim 39, wherein said component (A) is a member selectedfrom the group consisting of 2,2-bis(4-Cyanatophenyl) isopropylidene,Bisphenol F Cyanate ester, Bisphenol E Cyanate ester, Bisphenol MCyanate ester, dicyanate of Oxydiphenol, resorcinol Cyanate ester,Cyanated novolac, Cyanated phenol-dicyclopentadiene, diphenyl cyanateester, naphthol aralkyl Cyanate ester and mixtures thereof.
 41. Athermosetting resin composition as recited by claim 39, wherein saidcomponent (A) is defined by the formula

wherein X₁ and X₂ individually represent R, and R is a member selectedfrom the group consisting of —CH(CH₃)—, —CH₂—, —C(CH₃)₂—,dicyclopentadiene (DCP), and functionalized DCP; n is an integer greaterthan 1; and Y represents at least one functional group.
 42. Athermosetting resin composition as recited by claim 39, wherein saidcomponent (A) is defined by the formula:

wherein X₁ and X₂ individually represent at least alkyl groups, aromaticgroups, SO₂, O, or S; n is an integer greater than 1; and Y representsat least one functional group.
 43. A thermosetting resin composition asrecited by claim 42, wherein R is a member selected from the groupconsisting of —CH(CH₃)—, —CH₂—, —C(CH₃)₂—, dicyclopentadiene (DCP), andfunctionalized DCP.
 44. A thermosetting resin composition as recited byclaim 42, wherein Ar is a member selected from the group consisting of afunctionalized or non-functionalized benzene, biphenyl, naphthalene,phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, andbisphenol F novolac.
 45. A thermosetting resin composition as recited byclaim 42, wherein Y is a member selected from the group consisting ofhydrogen, aliphatic groups, aromatic groups, and halogens.
 46. Athermosetting resin composition as recited by claim 39, wherein saidcomponent (A) is defined by the formula

wherein X₁ and X₂ are alkyl groups, aromatic groups, SO₂, O, or S; n isan integer greater than 1; and Y represents at least one functionalgroup.
 47. A thermosetting resin composition as recited by claim 46,wherein R is a member selected from the group consisting of —CH(CH₃)—,—CH₂—, —C(CH₃)₂—, dicyclopentadiene (DCP), and functionalized DCP.
 48. Athermosetting resin composition as recited by claim 46, wherein Ar is amember selected from the group consisting of a functionalized ornon-functionalized benzene, biphenyl, naphthalene, phenol novolac,bisphenol A, bisphenol A novolac, bisphenol F, and bisphenol F novolac.49. A thermosetting resin composition as recited by claim 46, wherein Yis a member selected from the group consisting of hydrogen, aliphaticgroups, aromatic groups, and halogens.
 50. A thermosetting resincomposition as recited by claim 46, wherein said wherein X₂ is R, Ar,SO₂, O, or S.
 51. A thermosetting resin composition as recited by claim39, wherein Z has a wt % of at least 50% in reaction with component B.52. A thermosetting resin composition as recited by claim 39 comprisingsecondary reactive groups selected from the group consisting of allyls,vinyls, acrylates, halogens, ethoxys, and methoxys.
 53. A thermosettingresin composition as recited by claim 39, wherein R is a member selectedfrom the group consisting of OH, SH, NH₂, Allyl, Vinyl, Phenol,Anhydrides, Carboxylic acids and Acetylenes.
 54. A thermosetting resincomposition as recited by claim 39, wherein component B ranges fromabout 5%-50% by wt.
 55. A thermosetting resin composition as recited byclaim 39, wherein component B ranges from about 20%-35% by wt.
 56. Athermosetting resin composition as recited by claim 39, wherein contentof each component in said resin comprises 50-95 wt % component A, 5-50wt % component B, and up to 30 wt % flame-retardant.
 57. A thermosettingresin composition for use in prepregs/pre-impregnated composite fibersapplications defined by the formula:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B; “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A; wherein said thermosetting resin composition is formed bychemical reaction between: a. at least one cyanate ester component (A);and b. at least one reactive intermediate component (B), said componentB being capable of copolymerization with said component (A), saidcomponent (B) is a thermoplastic selected from the group consisting of(i) hydroxylated polybutadiene (HPBD) with molecular weights between 100and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD),(iii) reactive polydimethylsiloxane (PDMS) with molecular weightsbetween and including 100-20 000 g/mol and at least 2 functional groupsper molecule of either hydroxyl or epoxy groups, and (iv)polymethylphenylsiloxane containing between 3-9% OH functional groups;whereby said thermosetting resin composition does not undergo phaseseparation, but instead forms a neat, homogenous resin consisting of atriazine co-polymer that consists of component (A) and component (B)joined through a triazine moiety.
 58. A thermosetting resin compositionfor use in resin coated copper (RCC) applications defined by theformula:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B; “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A; wherein said thermosetting resin composition is formed bychemical reaction between: a. at least one cyanate ester component (A);and b. at least one reactive intermediate component (B), said componentB being capable of copolymerization with said component (A), saidcomponent (B) is a thermoplastic selected from the group consisting of(i) hydroxylated polybutadiene (HPBD) with molecular weights between 100and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD),(iii) reactive polydimethylsiloxane (PDMS) with molecular weightsbetween and including 100-20 000 g/mol and at least 2 functional groupsper molecule of either hydroxyl or epoxy groups, and (iv)polymethylphenylsiloxane containing between 3-9% OH functional groups;whereby said thermosetting resin composition does not undergo phaseseparation, but instead forms a neat, homogenous resin consisting of atriazine co-polymer that consists of component (A) and component (B)joined through a triazine moiety.
 59. A thermosetting resin compositionfor use in film adhesives defined by the formula:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B; “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A; wherein said thermosetting resin composition is formed bychemical reaction between: a. at least one cyanate ester component (A);and b. at least one reactive intermediate component (B), said componentB being capable of copolymerization with said component (A), saidcomponent (B) is a thermoplastic selected from the group consisting of(i) hydroxylated polybutadiene (HPBD) with molecular weights between 100and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD),(iii) reactive polydimethylsiloxane (PDMS) with molecular weightsbetween and including 100-20 000 g/mol and at least 2 functional groupsper molecule of either hydroxyl or epoxy groups, and (iv)polymethylphenylsiloxane containing between 3-9% OH functional groups;whereby said thermosetting resin composition does not undergo phaseseparation, but instead forms a neat, homogenous resin consisting of atriazine co-polymer that consists of component (A) and component (B)joined through a triazine moiety.
 60. A thermosetting resin compositionfor use in high frequency radomes defined by the formula:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B; “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A; wherein said thermosetting resin composition is formed bychemical reaction between: a. at least one cyanate ester component (A);and b. at least one reactive intermediate component (B), said componentB being capable of copolymerization with said component (A), saidcomponent (B) is a thermoplastic selected from the group consisting of(i) hydroxylated polybutadiene (HPBD) with molecular weights between 100and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD),(iii) reactive polydimethylsiloxane (PDMS) with molecular weightsbetween and including 100-20 000 g/mol and at least 2 functional groupsper molecule of either hydroxyl or epoxy groups, and (iv)polymethylphenylsiloxane containing between 3-9% OH functional groups;whereby said thermosetting resin composition does not undergo phaseseparation, but instead forms a neat, homogenous resin consisting of atriazine co-polymer that consists of component (A) and component (B)joined through a triazine moiety.
 61. A thermosetting resin compositionfor use in radio frequency (RF) laminates defined by the formula:T_(n)-[W—(Z)_(f)/(H)_(1-f)—W]_(n−1)—[W—(Z)_(f)/(H)_(1-f)—(OCN)_(f)/(R)_(1-f)]_(n+2)wherein “T” is a 1,3,5-substituted-triazine moiety (C₃N₃); “W” is alinking atom between triazine and either component A or component B; “Z”is component (A); “H” is component (B); “OCN” is cyanate ester endgroup; “R” is a reactive end group of component B; “n” is an integergreater than or equal to 1; and “f” is a weight or mole fraction ofcomponent A; wherein said thermosetting resin composition is formed bychemical reaction between: a. at least one cyanate ester component (A);and b. at least one reactive intermediate component (B), said componentB being capable of copolymerization with said component (A), saidcomponent (B) is a thermoplastic selected from the group consisting of(i) hydroxylated polybutadiene (HPBD) with molecular weights between 100and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD),(iii) reactive polydimethylsiloxane (PDMS) with molecular weightsbetween and including 100-20 000 g/mol and at least 2 functional groupsper molecule of either hydroxyl or epoxy groups, and (iv)polymethylphenylsiloxane containing between 3-9% OH functional groups;whereby said thermosetting resin composition does not undergo phaseseparation, but instead forms a neat, homogenous resin consisting of atriazine co-polymer that consists of component (A) and component (B)joined through a triazine moiety.